Abstract:

Disclosed is a fluorine-containing dicarboxylic acid represented by
formula (1),
##STR00001##
wherein n represents an integer of 1-4, and the two carboxylic groups are
not adjacent to each other on the aromatic ring. It is possible to obtain
a linear polymer compound by reacting the fluorine-containing
dicarboxylic acid with a comonomer (e.g., diaminodiol). By thermal
cyclization, this linear polymer compound can be converted into another
polymer compound having superior characteristics.

Claims:

1. A fluorine-containing dicarboxylic acid represented by formula (1),
##STR00052## wherein n represents an integer of 1-4, and the two
carboxylic groups are not adjacent to each other on the aromatic ring.

2. A fluorine-containing dicarboxylic acid according to claim 1, which is
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzene-dicarb-
oxylic acid.

3. A fluorine-containing dicarboxylic acid according to claim 1, which is
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzene-dicarb-
oxylic acid.

4. A fluorine-containing dicarboxylic acid according to claim 1, which is
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzene-dicarb-
oxylic acid.

5. A polymer compound obtained by reacting a fluorine-containing
dicarboxylic acid represented by formula (1), ##STR00053## wherein n
represents an integer of 1-4, and the two carboxylic groups are not
adjacent to each other on the aromatic ring, or an ester-forming
derivative of the fluorine-containing dicarboxylic acid,with a diol
represented by formula (2),HO--R1--OH (2)wherein R1 represents
an organic group that has a valence of at least two and that contains at
least one selected from the group consisting of aliphatic rings, aromatic
rings, condensed polycyclic aromatic rings, and heterocycles,R1 may
contain fluorine, chlorine, oxygen, sulfur or nitrogen,a part of hydrogen
atoms of R1 may be replaced with an alkyl group, fluoroalkyl group,
carboxyl group, hydroxy group, or cyano group,wherein the polymer
compound is represented by formula (6), ##STR00054## wherein n and
R1 are defined as above, the two --CO groups are not adjacent to
each other on the aromatic ring, and m represents a positive integer.

6. A polymer compound obtained by reacting a fluorine-containing
dicarboxylic acid represented by formula (1), ##STR00055## wherein n
represents an integer of 1-4, and the two carboxylic groups are not
adjacent to each other on the aromatic ring, or an amide-forming
derivative of the fluorine-containing dicarboxylic acid,with a diamine
represented by formula (3),H2N--R2--NH2 (3)wherein
R2 represents an organic group that has a valence of at least two
and that contains at least one selected from the group consisting of
aliphatic rings, aromatic rings, condensed polycyclic aromatic rings, and
heterocycles,R2 may contain fluorine, chlorine, oxygen, sulfur or
nitrogen,a part of hydrogen atoms of R2 may be replaced with an
alkyl group, fluoroalkyl group, carboxyl group, hydroxy group, or cyano
group,wherein the polymer compound is represented by formula (7),
##STR00056## wherein n and R2 are defined as above, the two --CO
groups are not adjacent to each other on the aromatic ring, and m
represents a positive integer.

7. A polymer compound obtained by reacting a fluorine-containing
dicarboxylic acid represented by formula (1), ##STR00057## wherein n
represents an integer of 1-4, and the two carboxylic groups are not
adjacent to each other on the aromatic ring, or an amide-forming
derivative of the fluorine-containing dicarboxylic acid,with a
diaminodiol represented by formula (4), ##STR00058## wherein R3
represents an organic group that has a valence of at least four and that
contains at least one selected from the group consisting of aliphatic
rings, aromatic rings, condensed polycyclic aromatic rings, and
heterocycles,R3 may contain fluorine, chlorine, oxygen, sulfur or
nitrogen,a part of hydrogen atoms of R3 may be replaced with an
alkyl group, fluoroalkyl group, carboxyl group, hydroxy group, or cyano
group,wherein the polymer compound is represented by formula (8),
##STR00059## wherein n and R3 are defined as above, the two --CO
groups are not adjacent to each other on the aromatic ring, and m
represents a positive integer.

8. A polymer compound obtained by reacting a fluorine-containing
dicarboxylic acid represented by formula (1), ##STR00060## wherein n
represents an integer of 1-4, and the two carboxylic groups are not
adjacent to each other on the aromatic ring, or an amide-forming
derivative of the fluorine-containing dicarboxylic acid,with a
diaminodiol represented by formula (5), ##STR00061## wherein R4
represents an organic group that has a valence of at least four and that
contains at least one selected from the group consisting of aliphatic
rings, aromatic rings, condensed polycyclic aromatic rings, and
heterocycles,R4 may contain fluorine, chlorine, oxygen, sulfur or
nitrogen,a part of hydrogen atoms of R4 may be replaced with an
alkyl group, fluoroalkyl group, carboxyl group, hydroxy group, or cyano
group,wherein the polymer compound is represented by formula (10),
##STR00062## wherein n and R4 are defined as above, the two --CO
groups are not adjacent to each other on the aromatic ring, and m
represents a positive integer.

9. A polymer compound that is obtained by a dehydration, ring-closing
reaction of a polymer compound represented by formula (8), ##STR00063##
wherein n represents an integer of 1-4,R3 represents an organic
group that has a valence of at least four and that contains at least one
selected from the group consisting of aliphatic rings, aromatic rings,
condensed polycyclic aromatic rings, and heterocycles,R3 may contain
fluorine, chlorine, oxygen, sulfur or nitrogen,a part of hydrogen atoms
of R3 may be replaced with an alkyl group, fluoroalkyl group,
carboxyl group, hydroxy group, or cyano group,the two --CO groups are not
adjacent to each other on the aromatic ring, andm represents a positive
integer,wherein the polymer compound is represented by formula (9),
##STR00064## wherein n, R3 and m are defined as above, and a main
chain of the polymer compound is not bonded to adjacent positions on the
aromatic ring.

10. A polymer compound obtained by a dehydration, ring-closing reaction of
a polymer compound represented by formula (10), ##STR00065## wherein n
represents an integer of 1-4,R4 represents an organic group that has
a valence of at least four and that contains at least one selected from
the group consisting of aliphatic rings, aromatic rings, condensed
polycyclic aromatic rings, and heterocycles,R4 may contain fluorine,
chlorine, oxygen, sulfur or nitrogen,a part of hydrogen atoms of R4
may be replaced with an alkyl group, fluoroalkyl group, carboxyl group,
hydroxy group, or cyano group,the two --CO groups are not adjacent to
each other on the aromatic ring, andm represents a positive
integer,wherein the polymer compound is represented by formula (11),
##STR00066## wherein n, R4 and m are defined as above, and a main
chain of the polymer compound is not bonded to adjacent positions on the
aromatic ring.

13. A process according to claim 12, wherein the carbonylation of the step
(c) is conducted by reacting
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
with carbon monoxide in the presence of a palladium catalyst and a basic
substance.

14. A process according to claim 12, wherein the carbonylation of the step
(c) is conducted by the steps of:(d) reacting
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
with an alkylmagnesium halide, metallic magnesium or alkyllithium, and(e)
reacting a product of the step (d) with carbon dioxide.

Description:

[0002]Polyester, polyamide, polyimide, and polybenzoxazole have been
developed as representatives of organic polymers having high heat
resistance. They form a large market in electronic device field,
engineering plastic field for automobile and aerospace uses, etc., fuel
cell field, medical material field, optical material field, etc. As their
center, various many polymers have been put into practical uses, such as
polyamides represented by nylon and Kevlar, polyacrylates used for liquid
crystal polymers, polyimides represented by Kapton, and polybenzoxazoles
represented by Zylon.

[0003]It is possible to produce polyester by a process by a
polycondensation between dicarboxylic acid and diol in the presence of a
condensing agent or by a process by converting dicarboxylic acid into an
acid chloride or ester, followed by a polycondensation with diol. It is
possible to produce polyamide by a process by a polycondensation between
dicarboxylic acid and diamine in the presence of a condensing agent or by
a process by converting dicarboxylic acid into a carboxylic chloride or
ester, followed by a polycondensation with diamine. It is possible to
produce polyimide by polymerizing diamine with tetracarboxylic
dianhydride, followed by a dehydration, ring-closing reaction. It is
possible to produce polybenzoxazole by a process by a polycondensation
between dicarboxylic acid and bisaminophenol in the presence of a
condensing agent and then a dehydration, ring-closing reaction.
Alternatively, it may be conducted by converting dicarboxylic acid into a
carboxylic chloride or ester, then a polycondensation with
bisaminophenol, and then a dehydration, ring-closing reaction.

[0004]In research and development of these resins, it has widely been
tried to introduce a hydroxy group(s), which is not directly involved in
the polymerization (polycondensation) and remains in the resin even after
the polycondensation, into the monomer to provide the resin with a
further function(s). For example, in Japanese Patent Application
Publication 2003-268233 A (Patent Publication 1), a phenolic hydroxy
group is introduced as a photosensitive group for providing the resin
with alkali solubility. In Japanese Patent Application Publication
2003-206352 A (Patent Publication 2), a phenolic hydroxy group is
introduced as an adhesive group for providing adhesion between fibers and
a resin matrix in a composite material. In International Publication WO
2007/010932 A1 or its corresponding Canadian Patent Application
Publication 2614648 A1 (Patent Publication 3), a phenolic hydroxy group
is introduced as a crosslinking point moiety.

[0005]The resin of Patent Publication 1 is described therein as a
polybenzoxazole. To produce this polybenzoxazole, there is conducted a
polycondensation between a bisaminophenol derivative (a polymerizable
monomer), in which an amino group and a phenolic hydroxy group are
adjacent to each other, and a dicarboxylic acid, thereby firstly
synthesizing a polyamidephenol precursor containing phenolic hydroxy
groups. The phenolic hydroxy group of this precursor serves as a
photosensitive group upon patterning by photolithography and then
disappears by the subsequent heating as the precursor is modified into an
oxazole ring of the final product.

[0006]In contrast, In Patent Publications 2 or 3, hydroxyl group is used
mainly as an adhesive group or crosslinking point moiety and partly
remains in the final product.

[0007]Recently, there have been active research and development in the
fields of photoresist material and the like by using fluorine-containing
compounds, which are superior in transparency in ultraviolet region,
particularly in vacuum ultraviolet region. In particular,
fluorine-containing hydroxy compounds (fluorocarbinols) are often used.
Fluorine is introduced as fluorocarbinol group to achieve adhesion to
substrate, high glass transition point, photosensitivity, while allowing
transparency at each wavelength for use, due to acidity of fluorocarbinol
group, alkali development property, and the like. Of fluorocarbinol
group, particularly hexafluoroisopropanol moiety (i.e.,
2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl group) attracts much
attention due to its dissolution behavior, anti-swelling property, and
high contrast, etc. Therefore, a lot of research and development is
conducted (see Journal of Photopolymer Science and Technology, Volume 17,
No. 14 (2004) pp. 609-619 (Non-patent Publication 1) and International
Publication WO 2006/070728 A1 or its corresponding European Patent
Application Publication EP 1832618 A1 (Patent Publication 4)).

[0008]Fluorine-containing compounds are under development and practical
use in the field of various materials, such as polyolefins and condensed
polymers, mainly in the field of advanced materials, due to
characteristics of fluorine, such as water repellency, oil repellency,
low water absorption, heat resistance, weather resistance, corrosion
resistance, transparency, photosensitivity, low refractive index, and
low-dielectric constant. In the field of condensed polymers, there are
proposals for introducing fluorine into diamine monomers, such as a
diamine monomer containing a fluorine atom(s) or trifluoromethyl group(s)
substituted for a hydrogen(s) of its benzene ring, a diamine monomer
containing a hexafluoroisopropenyl group introduced between two aromatic
rings, and a fluorine-containing diamine monomer in which a benzene ring
has been subjected to hydrogen reduction. Furthermore, a bishydroxyamine
monomer containing a hexafluoroisopropenyl group as a center atomic group
and aromatic hydroxyamines at its both sides is in practical use. In this
case, it is applied as polybenzoxazole or hydroxy-containing polyimide.

[0010]The polybenzoxazole resin of Patent Publication 1 has an
advantageous effect of lowering swelling in developing solution, as
compared with conventional polyimide resins using a carboxyl group in
polyamide acid as a developing solution-soluble group. However, as
mentioned above, since there is no phenolic hydroxy group remaining in
the final product, it is difficult to make the hydroxy group to
contribute to adhesion to substrate or the like.

[0011]In the cases of Patent Publications 2 and 3, a phenolic hydroxy
group remains in the final product. Therefore, it is possible to improve
adhesion to substrate and the like and to use the phenolic hydroxy group
in a cross-linking reaction with epoxy resin. On the other hand, the
phenolic hydroxy group remaining in the final product becomes a cause for
increasing hygroscopic property. Therefore, in the case of using it for
electronic material components such as LSI, it may cause the increase of
dielectric constant, cracks and the like.

[0012]Under such background, Patent Publication 4 proposes the
introduction of a hexafluoroisopropanol moiety (i.e.,
2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl group) in place of
phenolic hydroxy group. In fact, this publication discloses a synthesis
of polyamide or polyimide from a diamine containing hexafluoroisopropanol
moiety and a dicarboxylic acid or tetracarboxylic dianhydride. It is
mentioned that these polyamide and polyimide show lower dielectric
constant and lower water absorption, as compared with conventional
polymers derived from a diamine containing a phenolic hydroxy group(s).

[0013]The polymer of Patent Publication 4 is, however, characterized in
that an aromatic ring is bonded as a side chain to the main chain of the
polymer through an ester bond and that this aromatic ring has a
hexafluoroisopropanol moiety as a substituent. Although this polymer has
superior characteristics, a relatively bulky side chain is bonded to the
main chain through a hydrolysable ester bond, and acidic OH groups are
positioned at a terminal portion of the side chain. Therefore,
environment for its use is somewhat limited to sufficiently show its
capacities.

[0014]Furthermore, the synthesis of a diamine containing a
hexafluoroisopropanol moiety as a constituent component of the polymer of
Patent Publication 4 requires a relatively high cost. In the case of a
diamine containing a hexafluoroisopropanol moiety, the resin is limited
to a resin (e.g., polyamide, polyimide and polybenzoxazole) prepared by
the formation of amide bond as a polymerization elementary reaction, and
it cannot be used for synthesizing ester-series resins.

[0015]The polymers of Patent Publications 5 and 6 have a polyamide basic
skeleton containing a hexafluoroisopropanol moiety as an acidic alcohol,
and achieve high transparency, low dielectric constant, low water
absorption, heat resistance, weather resistance, corrosion resistance,
photosensitivity, and low refractive index, which are derived from
fluorine, while maintaining capabilities as heat resistant polymers. In a
final dehydration, ring-closing reaction (a thermal cyclization between a
OH group and an amide bond moiety) of the polymers, however, the OH group
disappears by incorporation into the resin skeleton. Therefore, it is
difficult in the final polymers after the thermal cyclization to
sufficiently maintain adhesion and compatibility with other resins, which
are derived from OH group.

[0016]Furthermore, imine by-products are produced in the productions of
diamine monomers of Patent Publications 5 and 6, and there occurs a load
of separating the imine by-product from the target polymer.

[0017]As an example that a hexafluoroisopropanol moiety has been
introduced into a dicarboxylic acid monomer, Patent Publication 7
discloses a phthalic derivative, which is defined as a dicarboxylic acid
derivative containing two carboxyl groups at ortho position of the
benzene nucleus. In this publication, an anhydride of a phthalic acid
derivative containing a hexafluoroisopropanol moiety is used as a curing
agent for epoxy resins. It is possible to convert this phthalic acid
derivative to other compounds by using reactivity of its anhydride. This
phthalic acid derivative is, however, not suitable for synthesizing
linear polymers such as polyester, polyamide and polybenzoxazole.

[0018]As mentioned above, there has been a demand for a linear polymer,
such as polyester, polyamide and polybenzoxazole, particularly a novel
aromatic polymer oriented to heat resistance, which has a repeating unit
derived from a dicarboxylic acid monomer having a hexafluoroisopropanol
moiety.

[0019]As a result of an eager examination to meet the above-mentioned
demand, the present inventors have reached a novel dicarboxylic acid
containing at least one hexafluoroisopropanol moiety in the molecule and
novel polymer compounds obtained by using the same.

[0020]That is, we have found a fluorine-containing dicarboxylic acid
represented by formula (1),

##STR00002##

[0021]wherein n represents an integer of 1-4, and the two carboxylic
groups are not adjacent to each other on the aromatic ring.

[0022]We have found that the fluorine-containing dicarboxylic acid has
properties that are significantly different from those of the
above-mentioned phthalic acid derivative (i.e., a dicarboxylic acid
derivative containing two carboxyl groups adjacent to each other on the
aromatic ring) of Patent Publication 7. In fact, we have found that the
fluorine-containing dicarboxylic acid can perform effectively as a unit
for synthesizing various linear polymers, such as polyester, polyamide
and polybenzoxazole.

[0023]That is, firstly, we have found a first polymer compound obtained by
reacting the fluorine-containing dicarboxylic acid or an ester-forming
derivative thereof with a diol represented by formula (2),

HO--R1--OH (2)

[0024]wherein R1 represents an organic group that has a valence of at
least two and that contains at least one selected from the group
consisting of aliphatic rings, aromatic rings, condensed polycyclic
aromatic rings, and heterocycles,

[0025]R1 may contain fluorine, chlorine, oxygen, sulfur or nitrogen,

[0026]a part of hydrogen atoms of R1 may be replaced with an alkyl
group, fluoroalkyl group, carboxyl group, hydroxy group, or cyano group.

[0027]The first polymer compound is represented by formula (6),

##STR00003##

[0028]wherein n and R1 are respectively defined as in formulas (1)
and (2), the two --CO groups are not adjacent to each other on the
aromatic ring, and m represents a positive integer.

[0029]Secondly, we have found a second polymer compound obtained by
reacting the fluorine-containing dicarboxylic acid or an amide-forming
derivative thereof with a diamine represented by formula (3),

H2N--R2--NH2 (3)

[0030]wherein R2 represents an organic group that has a valence of at
least two and that contains at least one selected from the group
consisting of aliphatic rings, aromatic rings, condensed polycyclic
aromatic rings, and heterocycles,

[0031]R2 may contain fluorine, chlorine, oxygen, sulfur or nitrogen,

[0032]a part of hydrogen atoms of R2 may be replaced with an alkyl
group, fluoroalkyl group, carboxyl group, hydroxy group, or cyano group.

[0033]The second polymer compound is represented by formula (7),

##STR00004##

[0034]wherein n and R2 are respectively defined as in formulas (1)
and (3), the two --CO groups are not adjacent to each other on the
aromatic ring, and m represents a positive integer.

[0035]Thirdly, we have found a third polymer compound obtained by reacting
the fluorine-containing dicarboxylic acid or an amide-forming derivative
thereof with a diaminodiol represented by formula (4),

##STR00005##

[0036]wherein R3 represents an organic group that has a valence of at
least four and that contains at least one selected from the group
consisting of aliphatic rings, aromatic rings, condensed polycyclic
aromatic rings, and heterocycles,

[0037]R3 may contain fluorine, chlorine, oxygen, sulfur or nitrogen,

[0038]a part of hydrogen atoms of R3 may be replaced with an alkyl
group, fluoroalkyl group, carboxyl group, hydroxy group, or cyano group.

[0039]The third polymer compound is represented by formula (8),

##STR00006##

[0040]wherein n and R3 are respectively defined as in formulas (1)
and (4), the two --CO groups are not adjacent to each other on the
aromatic ring, and m represents a positive integer.

[0041]Fourthly, we have found a fourth polymer compound obtained by
reacting the fluorine-containing dicarboxylic or an amide-forming
derivative thereof with a diaminodiol represented by formula (5),

##STR00007##

[0042]wherein R4 represents an organic group that has a valence of at
least four and that contains at least one selected from the group
consisting of aliphatic rings, aromatic rings, condensed polycyclic
aromatic rings, and heterocycles,

[0043]R4 may contain fluorine, chlorine, oxygen, sulfur or nitrogen,

[0044]a part of hydrogen atoms of R4 may be replaced with an alkyl
group, fluoroalkyl group, carboxyl group, hydroxy group, or cyano group.

[0045]The fourth polymer compound is represented by formula (10),

##STR00008##

[0046]wherein n and R4 are respectively defined as in formulas (1)
and (5), the two --CO groups are not adjacent to each other on the
aromatic ring, and m represents a positive integer.

[0047]Furthermore, we have found a fifth polymer compound obtained by a
dehydration, ring-closing reaction of the third polymer compound
represented by formula (8). The fifth polymer compound is represented by
formula (9),

##STR00009##

[0048]wherein n, R3 and m are respectively defined as in formulas
(1), (4) and (8), and a main chain of the polymer compound is not bonded
to adjacent positions on the aromatic ring.

[0049]Furthermore, we have found a sixth polymer compound obtained by a
dehydration, ring-closing reaction of the fourth polymer compound
represented by formula (10). The sixth polymer compound is represented by
formula (11),

##STR00010##

[0050]wherein n, R4 and m are respectively defined as in formulas
(1), (5) and (10), and a main chain of the polymer compound is not bonded
to adjacent positions on the aromatic ring.

[0051]The first to sixth polymer compounds according to the present
invention are resins characterized in that fluorine is contained and that
a free acidic OH group(s) exists in the vicinity of the polymer main
chain. Due to the existence of this acidic OH group, the resins show
superior photosensitivity, adhesion, compatibility with other resins (for
example, showing of a prompt and uniform alkali solubility), or
reactivity (for example, reactivity for serving as cross-linking points).

[0052]It is a great advantage that the OH group introduction does almost
not damage the first to sixth polymer compounds with respect to
characteristics derived from fluorine atom, such as low water absorption,
low dielectric constant, high weather resistance, high corrosion
resistance, transparency and low refractive index. This is supported by
the fact that the polymer compounds of the present invention show clearly
superior values in water absorption characteristics and dielectric
constant, as compared with their corresponding polymer compounds each
containing a phenolic hydroxy group (see the after-mentioned Examples and
Comparative Examples).

[0053]Of the above first to sixth polymer compounds, the fifth and sixth
polymer compounds each obtained by the above dehydration, ring-closing
reaction are useful substances, since they are particularly high in heat
resistance.

[0054]That is, we have succeeded in finding novel polymer compounds each
having (a) a heat resistance derived from a basic skeleton of the
polymer, (b) characteristics derived from fluorine atom, such as low
water absorption, low dielectric constant, high weather resistance, high
corrosion resistance, transparency, and low refractive index, (c)
characteristics derived from acidic OH group, such as photosensitivity,
adhesion, compatibility, and reactivity, and a good balance of these (a),
(b) and (c).

[0055]The fluorine-containing dicarboxylic acid represented by formula (1)
of the present invention contains at least one hexafluoroisopropanol
moiety introduced into dicarboxylic acid. With this, it became possible
to avoid the above-mentioned problem of imine by-product production upon
introducing a hexafluoroisopropanol moiety into diamine monomers in
Patent Publications 5 and 6.

[0056]Furthermore, we have found a simple process for producing
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid, which corresponds to the fluorine-containing dicarboxylic acid
represented by formula (1). This process (first process) includes the
step of carbonylating
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12),

[0061]with an alkylmagnesium halide, metallic magnesium or alkyllithium;
and

[0062](b) treating a product of the step (a) with hexafluoroacetone.

DETAILED DESCRIPTION

[0063]In the following, the present invention is exemplarily described in
detail by certain embodiments. A person skilled in the art may modify the
embodiments without deviating from the gist of the present invention. It
should be understood that such modification is in the scope of the
present invention.

NOVEL FLUORINE-CONTAINING DICARBOXYLIC ACID

[0064]As stated above, a novel fluorine-containing dicarboxylic acid
according to the present invention is represented by formula (1),

##STR00013##

[0065]wherein n represents an integer of 1-4, and the two carboxylic
groups are not adjacent to each other on the aromatic ring.

[0066]Specific examples of the fluorine-containing dicarboxylic acid
include

[0085]The fluorine-containing dicarboxylic acid represented by formula (1)
is preferably one wherein n is 1 or 2 due to its availability,
particularly preferably one wherein n is 1 due to its easy production.

[0086]It is an important point of the present invention that a phthalic
acid derivative (i.e., a dicarboxylic acid derivative in which two
carboxylic groups are adjacent to each other on the aromatic ring) is
excluded from the fluorine-containing dicarboxylic acid of the present
invention. In other words, the fluorine-containing dicarboxylic acid
represented by formula (1) is a compound in which two carboxylic groups
are at meta or para position. This position of the two carboxylic groups
unexpectedly provides the fluorine-containing dicarboxylic acid with good
polymerizability.

[0087]The process for synthesizing the fluorine-containing dicarboxylic
acid can be based on Journal of Organic Chemistry, 1965, Volume 30, pp.
998-1001 and U.S. Pat. No. 4,045,408. That is, as shown in the following
reaction formula [1], a xylene (o-xylene, m-xylene or p-xylene) is
reacted with hexafluoroacetone to introduce one to four
2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl groups. Then, the
methyl groups are oxidized by using an oxidizer (e.g., potassium
permanganate) to obtain the target dicarboxylic acid.

##STR00014##

[0088]wherein n represents an integer of 1-4, and x represents an
arbitrary number of 0-3.

[0089]By using the above process, it is possible to produce
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarbo-
xylic acid and
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid, which are novel dicarboxylic acids (see Examples 1 and 2).

[0090]As a use of the fluorine-containing dicarboxylic acid according to
the present invention, it can be polymerized to produce polymer
compounds. Since this fluorine-containing dicarboxylic acid represented
by formula (1) has at least one hexafluoroisopropanol moiety
(2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl group), it has at
least three functional groups at the same time in the molecule. These at
least three functional groups can effectively be used for producing
polymer compounds. Specifically, it is preferable to use reactivity of
dicarboxylic groups.

[0091]In formulas (6) to (11) of the polymer compounds of the present
invention, m (a positive integer) means the number of the repetitions of
the monomer unit in the polymer compound. It is preferably 5-10,000, more
preferably 10-1,000. The polymer compound of the present invention refers
to a mixture of polymer compounds having a certain range of the degree of
polymerization. It is preferably 1,000-5,000,000, particularly preferably
2,000-200,000, in weight average molecular weight. It is possible to set
the degree of polymerization and molecular weight of the polymer compound
at desired values by suitably adjusting the after-mentioned
polymerization conditions.

POLYESTER TYPE POLYMER COMPOUND

[0092]It is possible to conduct a polymerization by bringing the
dicarboxylic acid (a fluorine-containing polymerizable monomer)
represented by formula (1) into contact with a diol represented by
formula (2),

HO--R1--OH (2)

in a given range of temperature, thereby obtaining a polyester type
polymer compound represented by formula (6).

[0094]The polyester type polymer compound can be produced by using a
conventional polyester production process without particular limitation.
For example, the polymer compound represented by formula (6) can be
produced by a direct polycondensation (dehydrocondensation) between the
fluorine-containing dicarboxylic acid represented by formula (1) and the
diol represented by formula (2) in the presence of a condensing agent.
Furthermore, it is also possible to use an ester-forming derivative of
the fluorine-containing dicarboxylic acid. Herein, "ester-forming
derivative" refers to a compound that easily forms an ester bond with a
chemical reaction. In fact, the fluorine-containing dicarboxylic acid can
be converted into an ester-forming derivative, such as acid halide (e.g.,
dichloride and dibromide of the dicarboxylic acid), dialkylester (e.g.,
dimethyl ester and diethyl ester of the dicarboxylic acid), ester having
an active ester group (e.g., phenylester group, pyridylester group,
succinimide ester group), and mixed acid anhydride. Then, it is possible
to produce the polymer compound represented by formula (6) by reacting
such ester-forming derivative with the diol represented by formula (2).
In this case, it is also possible to use a polymer dissolution
accelerator (i.e., a metal salt such as lithium bromide and lithium
chloride) and a dehydrating agent such as sulfuric acid.

[0095]The process and the conditions of polymerization (polycondensation)
are not particularly limited. For example, it is possible to use a first
process in which an ester-forming derivative of the fluorine-containing
dicarboxylic acid and the diol are dissolved or melted with each other at
a temperature of 150° C. or higher to conduct the reaction without
solvent. It is possible to use a second process in which the reaction is
conducted in organic solvent at a high temperature (preferably
150° C. or higher). It is possible to use a third process in which
the reaction is conducted in organic solvent at a temperature of -20 to
80° C.

[0096]It is simplest to use a process by mixing an ester-forming
derivative of the fluorine-containing dicarboxylic acid represented by
formula (1) with the diol represented by formula (2) in organic solvent
to conduct the polycondensation. The molar ratio of this ester-forming
derivative to the diol may be 0.5 to 1.5, preferably 0.8 to 1.2. Similar
to normal polycondensation reactions, molecular weight of the obtained
polymer becomes larger as this molar ratio gets closer to 1.

[0097]The organic solvent usable in the polycondensation is not
particularly limited, as long as it can dissolve the both reactants. Its
examples include amide solvents (e.g., N,N-dimethylformamide,
N,N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide,
and N-methyl-2-pyrrolydone), aromatic solvents (e.g., benzene, anisole,
diphenyl ether, nitrobenzene, and benzonitrile), halogen-containing
solvents (e.g., chloroform, dichloromethane, 1,2-dichloroethane, and
1,1,2,2-tetrachloroethane), and lactones (e.g., γ-butyrolactone,
γ-valerolactone, δ-valerolactone, γ-caprolactone,
.di-elect cons.-caprolactone, and α-methyl-γ-butyrolactone.
It is effective to conduct the reaction under coexistence of an acid
acceptor (e.g., pyridine and triethylamine) with such organic solvent. In
particular, if the above amide solvent is used, the solvent itself
becomes an acid acceptor. With this, it is possible to obtain a polyester
resin that is high in degree of polymerization.

POLYAMIDE TYPE POLYMER COMPOUND

[0098]It is possible to conduct a polymerization by bringing the
dicarboxylic acid (a fluorine-containing polymerizable monomer)
represented by formula (1) into contact with a diamine represented by
formula (3),

H2N--R2--NH2 (3)

in a given range of temperature, thereby obtaining a polyamide type
polymer compound represented by formula (7).

[0100]The polyamide type polymer compound can be produced by using a
conventional polyamide production process without particular limitation.
For example, the polymer compound represented by formula (7) can be
produced by a direct polycondensation (dehydrocondensation) between the
fluorine-containing dicarboxylic acid represented by formula (1) and the
diamine represented by formula (3) in the presence of a condensing agent.
Furthermore, it is also possible to use an amide-forming derivative of
the fluorine-containing dicarboxylic acid. Herein, "amide-forming
derivative" refers to a compound that easily forms an amide bond with a
chemical reaction. In fact, the fluorine-containing dicarboxylic acid can
be converted into an amide-forming derivative, such as acid halide (e.g.,
dichloride and dibromide of the dicarboxylic acid), dialkylester (e.g.,
dimethyl ester and diethyl ester of the dicarboxylic acid), ester having
an active ester group (e.g., phenylester group, pyridylester group,
succinimide ester group), and mixed acid anhydride. Then, it is possible
to produce the polymer compound represented by formula (7) by reacting
such amide-forming derivative with the diamine represented by formula
(3). In this case, it is also possible to use a polymer dissolution
accelerator (i.e., a metal salt such as lithium bromide and lithium
chloride) and a dehydrating agent such as sulfuric acid.

[0101]The process and the conditions of polymerization (polycondensation)
are not particularly limited. For example, it is possible to use a first
process in which an amide-forming derivative of the fluorine-containing
dicarboxylic acid and the diamine are dissolved or melted with each other
at a temperature of 150° C. or higher to conduct the reaction
without solvent. It is possible to use a second process in which the
reaction is conducted in organic solvent at a high temperature
(preferably 150° C. or higher). It is possible to use a third
process in which the reaction is conducted in organic solvent at a
temperature of -20 to 80° C.

[0102]It is simplest to use a process by mixing an amide-forming
derivative of the fluorine-containing dicarboxylic acid represented by
formula (1) with the diamine represented by formula (3) in organic
solvent to conduct the polycondensation. The molar ratio of this
amide-forming derivative to the diamine may be 0.5 to 1.5, preferably 0.8
to 1.2. Similar to normal polycondensation reactions, molecular weight of
the obtained polymer becomes larger as this molar ratio gets closer to 1.

[0103]The organic solvent usable in the polycondensation is not
particularly limited, as long as it can dissolve the both reactants. Its
examples include the same organic solvents as those for producing the
polyester type polymer compound. It is effective to conduct the reaction
under coexistence of an acid acceptor (e.g., pyridine and triethylamine)
with such organic solvent. In particular, if the above amide solvent is
used, the solvent itself becomes an acid acceptor. With this, it is
possible to obtain a polyamide resin that is high in degree of
polymerization.

POLYAMIDE DIOL TYPE POLYMER COMPOUND

[0104]It is possible to conduct a polymerization by bringing the
dicarboxylic acid (a fluorine-containing polymerizable monomer)
represented by formula (1) into contact with a diaminodiol represented by
formula (4),

##STR00017##

in a given range of temperature, thereby obtaining a polyamide diol type
polymer compound represented by formula (8).

[0106]The polyamide diol type polymer compound can be produced by using a
conventional polyamide diol production process without particular
limitation. For example, the polymer compound represented by formula (8)
can be produced by a direct polycondensation (dehydrocondensation)
between the fluorine-containing dicarboxylic acid represented by formula
(1) and the diaminodiol represented by formula (4) in the presence of a
condensing agent. Furthermore, it is also possible to use an
amide-forming derivative of the fluorine-containing dicarboxylic acid. In
fact, the fluorine-containing dicarboxylic acid can be converted into an
amide-forming derivative, such as acid halide (e.g., dichloride and
dibromide of the dicarboxylic acid), dialkylester (e.g., dimethyl ester
and diethyl ester of the dicarboxylic acid), ester having an active ester
group (e.g., phenylester group, pyridylester group, succinimide ester
group), and mixed acid anhydride. Then, it is possible to produce the
polymer compound represented by formula (8) by reacting such
amide-forming derivative with the diaminodiol represented by formula (4).
In this case, it is also possible to use a polymer dissolution
accelerator (i.e., a metal salt such as lithium bromide and lithium
chloride) and a dehydrating agent such as sulfuric acid.

[0107]The process and the conditions of polymerization (polycondensation)
are not particularly limited. They may be the same as those for producing
the polyamide type polymer compound represented by formula (7), since
elementary reaction of the polymerization is an amide-forming reaction.
Furthermore, it is possible to use the same organic solvent as that for
producing the polyamide type polymer compound.

[0108]It is possible to subject the polyamide diol type polymer compound
to a dehydration, ring-closing reaction to convert it into a
polybenzoxazole type polymer compound represented by formula (9).

##STR00019##

[0109]It is possible to use a conventional dehydration, ring-closing
reaction without particular limitation. The cyclization can be conducted
by various methods for accelerating the dehydration condition, such as
heat, acid catalyst, and base catalyst. A heating ring-closing can be
conducted at a temperature of 80-400° C., particularly preferably
150-350° C. If the ring-closing temperature is lower than
150° C., the ring closing rate may become too low. This may damage
strength of the polybenzoxazole film. If it is higher than 350°
C., the coated film may become colored or brittle. The acid catalyst may
be selected from p-toluenesulfonic acid, methanesulfonic acid, etc. The
base catalyst may be selected from triethylamine, pyridine, etc. If the
polybenzoxazole after the ring closing is soluble in organic solvent, the
ring closing can chemically be conducted by using a dehydration reagent
(e.g., acetic anhydride) and an organic base (e.g., pyridine and
triethylamine).

[0110]It is possible by the cyclization (ring-closing) to conduct a resin
modification accompanied with considerable property changes, such as heat
resistance improvement, solubility change, lowering of refractive index
and dielectric constant, and occurrence of water repellency and oil
repellency.

HIGHLY FLUORINATED POLYAMIDE TYPE POLYMER COMPOUND

[0111]It is possible to conduct a polymerization by bringing the
dicarboxylic acid (a fluorine-containing polymerizable monomer)
represented by formula (1) into contact with a diaminodiol represented by
formula (5),

##STR00020##

in a given range of temperature, thereby obtaining a highly fluorinated
polyamide type polymer compound represented by formula (10).

##STR00021##

[0112]Specific examples of the diaminodiol represented by formula (5)
having two hexafluoroisopropanol moieties include the following
compounds.

##STR00022## ##STR00023## ##STR00024##

[0113]The highly fluorinated polyamide type polymer compound can be
produced by using a conventional polyamide production process without
particular limitation. For example, the polymer compound represented by
formula (10) can be produced by a direct polycondensation
(dehydrocondensation) between the fluorine-containing dicarboxylic acid
represented by formula (1) and the diaminodiol represented by formula (5)
in the presence of a condensing agent. Furthermore, it is also possible
to use an amide-forming derivative of the fluorine-containing
dicarboxylic acid. In fact, the fluorine-containing dicarboxylic acid can
be converted into an amide-forming derivative, such as acid halide (e.g.,
dichloride and dibromide of the dicarboxylic acid), dialkylester (e.g.,
dimethyl ester and diethyl ester of the dicarboxylic acid), ester having
an active ester group (e.g., phenylester group, pyridylester group,
succinimide ester group), and mixed acid anhydride. Then, it is possible
to produce the polymer compound represented by formula (10) by reacting
such amide-forming derivative with the diaminodiol represented by formula
(5). In this case, it is also possible to use a polymer dissolution
accelerator (i.e., a metal salt such as lithium bromide and lithium
chloride) and a dehydrating agent such as sulfuric acid.

[0114]The process and the conditions of polymerization (polycondensation)
are not particularly limited. They may be the same as those for producing
the polyamide type polymer compound represented by formula (7), since
elementary reaction of the polymerization is an amide-forming reaction.
Furthermore, it is possible to use the same organic solvent as that for
producing the polyamide type polymer compound.

[0115]It is possible to subject the highly fluorinated polyamide type
polymer compound to a dehydration, ring-closing reaction to convert it
into a heterocyclic type polymer compound represented by formula (11)

##STR00025##

[0116]The conditions for conducting the dehydration, ring-closing reaction
are not particularly limited. The cyclization can be conducted by various
methods for accelerating the dehydration condition, such as heat, acid
catalyst, and base catalyst. It is possible to achieve the dehydration,
ring-closing under a milder condition than that for forming the oxazole
ring of formula (9).

[0117]The heterocyclic polymer compound represented by formula (11) shows
a lower dielectric constant, a lower water absorption and a higher
transparency than the polybenzoxazole represented by formula (9) does,
since the former contains hetero rings with trifluoromethyl groups.

[0118]It is possible to use the fluorine-containing polymer of the present
invention in the form of varnish, where it is dissolved in organic
solvent, powder, film, or solid. According to need, it is optional to add
a suitable additive (e.g., oxidation stabilizer, filler, silane coupling
agent, photosensitizing agent, photo polymerization initiator, and
sensitizer) to the polymer obtained. In using the polymer in the form of
varnish, it can be applied onto a substrate (e.g., glass, silicon wafer,
metal, metal oxide, ceramic, and resin) by a normal method (e.g., spin
coating, spraying, flow coating, impregnation coating, and brush
coating).

[0119]As stated above, it is possible to obtain
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,2-benzenedicarbo-
xylic acid (see Journal of Organic Chemistry, 1965, Vol. 30, pp. 998-1001;
U.S. Pat. No. 4,045,408; and the following reaction formula [2]) by a
process in which a starting material of o-xylene is reacted with
hexafluoroacetone to introduce a
2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl group, and then the
two methyl groups are oxidized by using an oxidizing agent (e.g.,
potassium permanganate). Similarly, it is possible to obtain
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid (see Example 1 and the following reaction formula [3]) by
replacing o-xylene with m-xylene. Similarly, it is possible to obtain
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarbo-
xylic acid (see Example 2 and the following reaction formula [4]) by
replacing o-xylene with p-xylene.

##STR00026##

[0120]As stated above, however, it is difficult to synthesize linear
polymers, such as polyester, polyamide and polybenzoxazole, particularly
aromatic polymers oriented to heat resistance, from
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,2-benzenedicarbo-
xylic acid, which is obtained by Reaction Formula [2] and is not according
to the present invention.

[0121]In contrast, each of
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid and
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarbo-
xylic acid, which are respectively obtained by Reaction Formulas [3] and
[4] and are according to the present invention, has a higher linearity
and thereby suitably functions as a structural unit of various polymers.

[0122]From the viewpoint of symmetry, however, it is considered that
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid represented by the following formula,

##STR00027##

is a more superior structural unit. The process for producing a compound
having such structure has not been known up to now. This compound cannot
be produced by a process in which m-xylene is reacted with
hexafluoroacetone (see Reaction Formula [3]), due to the problem of
orientation.

[0123]As a result of further research, we have found a process for
producing the target
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid by using a trihalobenzene as the starting material by referring
to Journal of Organometallic Chemistry, Vol. 215, 1981, pp. 281-291.

[0132]Specific examples of the 1,3,5-trihalobenzene used in the step (a)
include 1,3,5-trifluorobenzene, 1,3,5-tricholorobenzene,
1,3,5-tribromobenzene, 1,3,5-triiodobenzene,
1,3,5-tris(trifluoromethanesulfonyl)benzene,
1,3,5-tri(methanesulfonyl)benzene, 1,3,5-tri(benzenesulfonyl)benzene, and
1,3,5-tri(p-tosylsulfonyl)benzene. Of these, 1,3,5-tricholorobenzene,
1,3,5-tribromobenzene and 1,3,5-triiodobenzene are preferable, and
1,3,5-tribromobenzene is particularly preferable.

[0133]The step (a) may be conducted by a first reaction in which the
1,3,5-trihalobenzene is reacted with an alkylmagnesium halide represented
by formula (14)

R'MgZ (14)

[0134]wherein R' represents an alkyl group, and Z represents a halogen
that is chlorine, bromine or iodine. The alkyl group R' may be
straight-chain or branched and may be a C1-C8 alkyl group. Its
specific examples include ethyl group, propyl group, isopropyl group,
butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group,
heptyl group, octyl group, and 2-ethylhexyl group. The halogen Z is
preferably a chlorine atom or bromine atom.

[0135]The first reaction may be conducted in a suitable solvent,
preferably under an inert gas atmosphere, to obtain
3,5-dihalophenylmagnesium halide (see Scheme 1).

[0136]The amount of the alkylmagnesium halide by mol may be 0.3 to 5
times, preferably 1 to 2 times, that of the 1,3,5-trihalobenzene
represented by formula (13).

[0137]In the first reaction, the solvent is preferably an ether series
solvent. Its specific examples include diethyl ether, diisopropyl ether,
t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, and
dioxane. The amount of the solvent by volume may be 0.5 to 10 times,
preferably 1 to 5 times, that of the 1,3,5-trihalobenzene represented by
formula (13). The inert gas is preferably nitrogen gas or argon gas.

[0138]The reaction temperature for conducting the first reaction may be in
a range of 0° C. to around the reflux temperature of the solvent,
preferably 0° C. to 65° C., more preferably 10° C.
to 40° C.

[0139]The reaction time for conducting the first reaction is not
particularly limited. The optimum reaction time may vary depending on
temperature and the amount of the substrate used. Therefore, it is
preferable to conduct the reaction, while monitoring progress of the
reaction by a general-purpose analytical means, such as gas
chromatography, and to terminate the first reaction after confirming that
the raw material has sufficiently been consumed.

[0140]The alkylmagnesium halide may be a commercial product or one
produced upon conducting the first reaction.

[0141]The step (a) may be conducted by a second reaction in which the
1,3,5-trihalobenzene represented by formula (13) is reacted with metallic
magnesium in a suitable solvent, preferably under an inert gas
atmosphere, to obtain 3,5-dihalophenylmagnesium halide (see Scheme 1).

[0142]The metallic magnesium may be in any form such as bulky form, tape
form, foil form, flake form, shave form, or powder form. From the point
of reactivity, it is preferably flake form, shave form or powder form,
particularly preferably powder form. The amount of the metallic magnesium
by mol may be 0.8 to 5 times, preferably 1 to 2 times, that of the
1,3,5-trihalobenzene represented by formula (13).

[0143]In the second reaction, the solvent is preferably an ether series
solvent. Its specific examples include diethyl ether, diisopropyl ether,
t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, and
dioxane. The amount of the solvent by volume may be 0.5 to 10 times,
preferably 1 to 5 times, that of the 1,3,5-trihalobenzene represented by
formula (13). The inert gas is preferably nitrogen gas or argon gas.

[0144]The reaction temperature for conducting the second reaction may be
in a range of 0° C. to around the reflux temperature of the
solvent, preferably 0° C. to 100° C., more preferably
10° C. to 80° C.

[0145]The reaction time for conducting the second reaction is not
particularly limited. The optimum reaction time may vary depending on
temperature and the amount of the substrate used. Therefore, it is
preferable to conduct the reaction, while monitoring progress of the
reaction by a general-purpose analytical means, such as gas
chromatography, and to terminate the second reaction after confirming
that the raw material has sufficiently been consumed.

[0146]The step (a) may be conducted by a third reaction in which the
1,3,5-trihalobenzene is reacted with an alkyllithium represented by
formula (16),

[0151]These solvents may be used singly or in a mixture of at least two.
The amount of the solvent by volume may be 0.5 to 10 times, preferably 1
to 5 times, that of the 1,3,5-trihalobenzene represented by formula (13).
The inert gas is preferably nitrogen gas or argon gas.

[0152]The reaction temperature for conducting the third reaction may be
-150° C. to 200° C., preferably -110° C. to around
the reflux temperature of the solvent.

[0153]The reaction time for conducting the third reaction is not
particularly limited. The optimum reaction time may vary depending on
temperature and the amount of the substrate used. Therefore, it is
preferable to conduct the reaction, while monitoring progress of the
reaction by a general-purpose analytical means, such as gas
chromatography, and to terminate the third reaction after confirming that
the raw material has sufficiently been consumed.

[0154]The alkyllithium may be a commercial product or one produced upon
conducting the third reaction.

[0155]The step (b) is conducted by reacting an intermediate obtained by
the step (a) with hexafluoroacetone (see Scheme 1).

[0156]The intermediate obtained by each of the first to third reactions of
the step (a) is a highly reactive, unstable substance. Therefore, it is
normal to subject the reaction liquid after the step (a) to the step (b)
without conducting a purification to isolate the intermediate.

[0157]In the step (b), hexafluoroacetone (boiling point: -28° C.)
may be bubbled as gas into the reaction liquid or may be added as liquid
by cooling. It is, however, necessary to use a hexafluoroacetone that is
sufficiently dry and contains no water. Its hydrate is of no use.

[0158]In the case of using hexafluoroacetone as gas, it is preferable to
use an apparatus (a cooling apparatus or sealed reactor) for preventing
leak of hexafluoroacetone. The apparatus is particularly preferably a
sealed reactor.

[0159]The step (b) may be conducted at a temperature of -200° C. to
50° C., preferably -150° C. to room temperature,
particularly preferably -100° C. to room temperature. If it is
lower than -200° C., it may be difficult to conduct the reaction.
If it is higher than 50° C., side reactions may occur.

[0160]It is preferable to conduct the step (b) by using solvent. The
solvent to be used is not particularly limited, as long as it is not
involved in the reaction. As stated above, it is possible to easily
conduct the step (b) by adding hexafluoroacetone to the reaction liquid
after the step (a). Therefore, it is preferable to use the solvent itself
used in the step (a).

[0161]The reaction time for conducting the step (b) is not particularly
limited. The optimum reaction time may vary depending on temperature and
the amount of the substrate used. Therefore, it is preferable to conduct
the reaction, while monitoring progress of the reaction by a
general-purpose analytical means, such as gas chromatography, and to
terminate the reaction after confirming that the raw material has
sufficiently been consumed.

[0162]After the step (b), it is possible to obtain
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12) by a normal means such as extraction,
distillation or crystallization. According to need, it can be purified by
column chromatography, recrystallization, etc.

[0163]The step (c) is conducted by carbonylating
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene,
which is represented by formula (12), into
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid. This carbonylation may be conducted as shown in Scheme 2.

##STR00031##

[0164]As shown in Scheme 2, the step (c) may be conducted by two steps of
(d) and (e).

[0165]The step (d) may be conducted by a first reaction in which
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene,
which is represented by formula (12), is reacted with an alkylmagnesium
halide represented by formula (14)

R'MgZ (14)

[0166]wherein R' represents an alkyl group, and Z represents a halogen
that is chlorine, bromine or iodine. The alkyl group R' may be
straight-chain or branched and may be a C1-C8 alkyl group. Its
specific examples include ethyl group, propyl group, isopropyl group,
butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group,
heptyl group, octyl group, and 2-ethylhexyl group. The halogen Z is
preferably a chlorine atom or bromine atom.

[0167]The first reaction may be conducted in a suitable solvent,
preferably under an inert gas atmosphere, to obtain a Grignard reagent
(see Scheme 2).

[0168]The amount of the alkylmagnesium halide by mol may be 1 to 10 times,
preferably 2 to 4 times, that of the
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12).

[0169]In the first reaction, the solvent is preferably an ether series
solvent. Its specific examples include diethyl ether, diisopropyl ether,
t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, and
dioxane. The amount of the solvent by volume may be 0.5 to 10 times,
preferably 1 to 5 times, that of the
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12). The inert gas is preferably nitrogen gas or
argon gas.

[0170]The reaction temperature for conducting the first reaction may be in
a range of 0° C. to around the reflux temperature of the solvent,
preferably 0° C. to 65° C., more preferably 10° C.
to 40° C. The reaction time may be 1 to 48 hours. The
alkylmagnesium halide may be a commercial product or one produced upon
conducting the first reaction.

[0171]The step (d) may be conducted by a second reaction in which the
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12) is reacted with metallic magnesium in a
suitable solvent, preferably under an inert gas atmosphere, to obtain a
Grignard reagent (see Scheme 2).

[0172]The metallic magnesium may be in any form such as bulky form, tape
form, foil form, flake form, shave form, or powder form. From the point
of reactivity, it is preferably flake form, shave form or powder form,
particularly preferably powder form. The amount of the metallic magnesium
by mol may be 1 to 10 times, preferably 2 to 5 times, that of the
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12).

[0173]In the second reaction, the solvent is preferably an ether series
solvent. Its specific examples include diethyl ether, diisopropyl ether,
t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, and
dioxane. The amount of the solvent by volume may be 0.5 to 10 times,
preferably 1 to 5 times, that of the
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12). The inert gas is preferably nitrogen gas or
argon gas.

[0174]The reaction temperature for conducting the second reaction may be
in a range of 0° C. to around the reflux temperature of the
solvent, preferably 0° C. to 100° C., more preferably
10° C. to 80° C. The reaction time may be 1 to 48 hours.

[0175]The step (d) may be conducted by a third reaction in which the
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12) is reacted with an alkyllithium represented
by formula (16),

[0177]The third reaction may be conducted in a suitable solvent,
preferably under an inert gas atmosphere, to obtain an organic lithium
reagent (see Scheme 2).

[0178]The amount of the alkyllithium by equivalent may be 1 to 10 times,
preferably 2 to 5 times, that of the
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12).

[0180]These solvents may be used singly or in a mixture of at least two.
The amount of the solvent by volume may be 0.5 to 10 times, preferably 1
to 5 times, that of the
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12). The inert gas is preferably nitrogen gas or
argon gas.

[0181]The reaction temperature for conducting the third reaction may be
-150° C. to 200° C., preferably -110° C. to around
the reflux temperature of the solvent. The reaction time may be 1 to 48
hours. The alkyllithium may be a commercial product or one produced upon
conducting the third reaction.

[0182]The step (e) is a carbonylation of an intermediate (i.e., the
Grignard reagent or organic lithium reagent) obtained by the step (d)
into the target
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid by carbon dioxide as a carbonylation agent (see Scheme 2).

[0183]In the step (e), the form of carbon dioxide under ordinary
temperature and ordinary pressure is not particularly limited, and it may
take a gas or solid form. A skilled person in the art can select a
suitable form.

[0184]In the case of replacing the atmosphere of the reaction system with
carbon dioxide in the form of gas, the reaction can be conducted under a
pressurized condition. In this case, a reactor is charged with the
reaction liquid obtained by the step (e), followed by tightly closing the
reactor.

[0185]In the case of using carbon dioxide (dry ice) in the form of solid,
the reaction can be conducted under ordinary pressure due to its easy
handling.

[0186]The carbonylation is conducted by heating with or without stirring.
In the case of conducting the reaction under pressurized condition, the
pressure may be 0.1 to 1.2 kPa, preferably 0.5 to 1.0 kPa, more
preferably 0.5 to 0.8 kPa. If it is lower than 0.1 kPa, the reaction may
not proceed sufficiently, thereby causing low yield or necessity of a
long time to complete the reaction due to low reaction rate. Even if it
is higher than 1.2 kPa, there occurs almost no change in reaction rate
and yield of the target product in the carbonylation. Therefore, it is
not preferable.

[0187]As the reactor for conducting the reaction under pressurized
condition, it is possible to use a metal container such as stainless
steel, Hastelloy and Monel metal. In the case of conducting the reaction
under ordinary pressure, a skilled person in the art can suitably select
the reactor.

[0188]The reaction temperature upon adding carbon dioxide in the form of
gas or solid (dry ice) may be -150° C. to 200° C.,
preferably -110° C. to around the reflux temperature of the
solvent used.

[0189]As an alternative to the two steps (d) and (e), the step (c) may be
conducted by one step in which
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12) is reacted with carbon monoxide as a
carbonylation agent in the presence of a palladium catalyst and a basic
substance (see Scheme 2). This reaction is described in detail in the
following.

[0191]Each of these palladium catalysts shows a satisfactory catalytic
activity. It is economically particularly preferable to use a bivalent
palladium complex, such as palladium chloride, palladium acetate,
PdCl2[P(Ph)3]2, and
PdCl2[P(Ph)2CH2CH2CH2CH2P(Ph)2], which
have low prices and are easy in handling.

[0192]The amount of the palladium catalyst may be 0.00001 to 0.2 moles,
preferably 0.001 to 0.1 moles, more preferably 0.001 to 0.05 moles, per
mol of 5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalob-
enzene represented by formula (12).

[0193]It is particularly preferable to use a trivalent phosphorus compound
as a promoter to maintain activity of the palladium catalyst. Herein, the
promoter refers to a substance that is added in a small amount to
increase activity or selectivity of the catalyst.

[0194]A preferable compound as the promoter is represented by formula
(16),

[0196]Another preferable compound as the promoter is a phosphine
represented by formula (17),

(R5)2P-Q-P(R6)2 (17)

[0197]wherein R5 and R6 are defined as in formula (16), and Q
represents an alkylene group --(CH2)m-- where m represents an
integer of 1-8, preferably 1-4. Specific examples of this phosphine
include 1,1'-bis(diphenylphosphino)ferrocene,
1,4-bis(diphenylphosphino)butane, 1,3-bis(diphenylphosphino)propane,
1,2-bis(diphenylphosphinoethane.

[0198]The amount of the trivalent phosphorus compound may be 0.5 to 50
moles per mol of the palladium catalyst. Herein, the trivalent phosphorus
compound may be in a first form that is a free compound by itself or in a
second form (e.g., PdCl2[P(Ph)3]2) in which it has already
been incorporated as a ligand into a palladium catalyst. It is optional
to use the first and second forms at the same time.

[0199]The basic substance used in the step (c) is not particularly
limited, but it is preferably a basic substance such that pH becomes 8 or
greater. Its specific examples include inorganic bases (e.g., ammonia,
sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium
carbonate, potassium hydrogencarbonate, and potassium hydroxide), and
organic bases such as tertiary amines (e.g., trimethylamine,
triethylamine, tripropylamine, and tributylamine), secondary amines
(e.g., diethylamine and dipropylamine), and primary amines (e.g.,
propylamine and butylamine). Of these, a preferable one is an organic
amine that is a base having a middle strength. Its specific examples
include methylamine, ethylamine, isopropylamine, n-butylamine,
dimethylamine, diethylamine, triethylamine, di-isopropylethylamine,
di-n-butylamine, tri-n-butylamine, tetramethylethylenediamine,
N,N-dimethylaniline, N,N-diethylaniline, pyridine, lutidine,
2-methylpyridine, N-methylmorpholine, pyperidine, pyrrolydine,
morpholine, dibutylamine, and diisopropylamine. Of these, triethylamine
is particularly preferable.

[0200]The amount of the basic substance may be 1-50 moles, preferably 1-20
moles, more preferably 1-10 moles, per mol of
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12). The reaction is conducted normally in an
inert gas such as nitrogen or argon. In general, the reaction temperature
may be -50° C. to 160° C., preferably -10° C. to
100° C., more preferably -5° C. to 50° C.

[0201]The step (c) as one step is conducted preferably in the presence of
solvent. The solvent is not particularly limited as long as it is not
involved in the reaction. Its specific examples include aromatics (e.g.,
n-pentane, n-hexane, n-heptane, and n-octane), ethers (e.g., diethyl
ether, tetrahydrofuran, and dioxane), halogenated hydrocarbons (e.g.,
dichloromethane and chloroform), alkylketones (e.g., acetone), alcohols
(e.g., methanol, ethanol, ethylene glycol, diethylene glycol, and
glycerol), aprotic polar solvents (e.g., acetonitrile,
N,N-dimethylformamide (DMF), dimethylsufoxide (DMSO), and
hexamethylphosphoric triamide (HMPA)) and water. Of these, preferable
ones are ethers (e.g., diethyl ether, tetrahydrofuran, and dioxane) and
alcohols (e.g., methanol, ethanol, ethylene glycol, diethylene glycol,
and glycerol). A particularly preferable one is water. These solvents may
be used singly or in combination of at least two. The amount of the
solvent by volume may be 0.5 to 10 times, preferably 1 to 7 times, that
of 5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenze-
ne represented by formula (12).

[0202]The reaction temperature of the step (c) as one step is not
particularly limited. It may be -50° C. to 200° C.,
preferably -10° C. to 180° C., more preferably -5°
C. to 150° C.

[0203]As stated above, carbon monoxide is used as a carbonylation agent.
The reaction can be conducted under pressurized condition in the case of
replacing atmosphere of the reaction system with carbon monoxide. The
reaction is conducted by firstly charging the reactor with
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene
represented by formula (12), palladium catalyst, basic substance and
solvent and then tightly closing the reactor.

[0204]The carbonylation is conducted by heating with or without stirring.
In the case of conducting the reaction under pressurized condition, the
pressure may be 0.1 to 1.2 kPa, preferably 0.5 to 1.0 kPa, more
preferably 0.5 to 0.8 kPa. If it is lower than 0.1 kPa, the reaction may
not proceed sufficiently, thereby causing low yield or necessity of a
long time to complete the reaction due to low reaction rate. Even if it
is higher than 1.2 kPa, there occurs almost no change in reaction rate
and yield of the target product in the carbonylation. Therefore, it is
not preferable.

[0205]As the reactor for conducting the reaction under pressurized
condition, it is possible to use a metal container such as stainless
steel, Hastelloy and Monel metal.

[0206]The post treatment after the reaction of the step (c) by the
above-described two steps (d) and (e) or by the above-described one step
(c) may be conducted by a normal post treatment of organic syntheses. For
example, it is possible to conduct the post treatment by adding the
reaction liquid to a hydrochloric acid aqueous solution, followed by
extraction with an organic solvent (e.g., ethyl acetate, toluene, and
methylene chloride), then removing water from the organic layer with
dehydrator or the like, and then distilling the solvent off, thereby
obtaining a crude product of
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid.

[0207]It is possible to conduct a further post treatment as a particularly
preferable embodiment by adding an inorganic base (e.g., sodium
hydroxide) aqueous solution to the above crude product to dissolve it as
a benzoate in the aqueous solution, followed by extracting organic
impurities with an organic solvent (e.g., hexane and heptane), then
making the remaining aqueous solution acidic by using an acid (e.g.,
hydrochloric acid), then extraction with an organic solvent (e.g., ethyl
acetate, toluene, and methylene chloride), then removing water with
dehydrator or the like, and then distilling the solvent off, thereby
obtaining a purified product of
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid.

[0208]The following nonlimitative examples are illustrative of the present
invention.

[0209]A 1 L reactor was charged under nitrogen with 100.0 g (0.94 mol) of
m-xylene and 6.3 g (0.047 mol/0.05 eq) of aluminum chloride, followed by
adjusting the inside temperature to 10° C. Then, 164.2 g (0.99
mol/1.05 eq) of hexafluoroacetone was introduced in a temperature range
of 10-25° C. After the introduction, stirring was conducted at
room temperature for 1 hr. Then, 100 mL of 10% hydrochloric acid was
added. The resulting aqueous layer was extracted two times with 40 mL of
chloroform. The resulting organic layers were combined together, followed
by removing water with anhydrous magnesium sulfate, filtration,
concentration, and vacuum distillation, thereby obtaining 227.6 g of
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dimethylbenzen-
e represented by the following formula. Upon this, purity was 95%, and
yield was 84%.

##STR00032##

[0210]The properties of the obtained
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dimethylbenzen-
e were as follows.

[0213]A 300 mL reactor was charged with 10.0 g (36.7 mmol) of the obtained
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dimethylbenzen-
e (purity: 95%) and 150 mL of 0.15N NaOH, followed by heating to
85° C. Then, 26.1 g (165.3 mmol/4.7 eq) of potassium permanganate
was gradually added by spending 1 hr, followed by stirring at 90°
C. for 4 hr. After the reaction, 11 mL of concentrated hydrochloric acid
was added, followed by discoloring with sodium sulfite and extraction
with 200 mL of diisopropyl ether. Furthermore, the aqueous layer was
extracted two times with 50 mL of diisopropyl ether. The combined organic
layer was dehydrated with anhydrous magnesium sulfate, followed by
filtration, concentration and drying, thereby obtaining a pale yellow
powder. To the obtained pale yellow powder 30 mL of toluene and 4 mL of
acetonitrile were added, followed by reflux and cooling to conduct
recrystallization, thereby obtaining 6.1 g of the target
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid represented by the following formula. Upon this, yield was 50%,
and purity was 99.5%.

##STR00033##

[0214]The properties of the obtained
4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid were as follows.

[0218]A 1 L reactor was charged under nitrogen with 200.0 g (1.88 mol) of
p-xylene and 12.5 g (0.094 mol/0.06 eq) of aluminum chloride, followed by
adjusting the inside temperature to 18° C. Then, 327.7 g (1.97
mol/1.06 eq) of hexafluoroacetone was introduced in a temperature range
of 18-25° C. After the introduction, stirring was conducted at
room temperature for 3 hr. Then, 200 mL of 10% hydrochloric acid was
added. The resulting aqueous layer was extracted two times with 50 mL of
chloroform. The resulting organic layers were combined together, followed
by removing water with anhydrous magnesium sulfate, filtration,
concentration, and vacuum distillation, thereby obtaining 451.3 g of
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-dimethylbenzen-
e represented by the following formula. Upon this, purity was 92%, and
yield was 81%.

##STR00034##

[0219]The properties of the obtained
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-dimethylbenzen-
e were as follows.

[0222]A 5 L reactor was charged with 200.0 g (0.676 mol) of the obtained
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-dimethylbenzen-
e (purity: 92%) and 3.0 L of 0.15N NaOH, followed by heating to 85°
C. Then, 480.7 g (3.04 mol/4.5 eq) of potassium permanganate was
gradually added by spending 3 hr, followed by stirring at 90° C.
for 4 hr. After the reaction, 200 mL of concentrated hydrochloric acid
was added, followed by discoloring with sodium sulfite and extraction
with 1.4 L of diisopropyl ether. Furthermore, the aqueous layer was
extracted two times with 500 mL of diisopropyl ether. The combined
organic layer was dehydrated with anhydrous magnesium sulfate, followed
by filtration, concentration and drying, thereby obtaining a pale yellow
powder. To the obtained pale yellow powder 560 mL of toluene and 80 mL of
acetonitrile were added, followed by reflux and cooling to conduct
recrystallization, thereby obtaining 131.1 g of the target
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarbo-
xylic acid represented by the following formula. Upon this, yield was 58%,
and purity was 99.8%.

##STR00035##

[0223]The properties of the obtained
2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarbo-
xylic acid were as follows.

[0227]Under nitrogen atmosphere, a 500 mL glass flask was charged with
30.0 g (95.0 mmol) of 1,3,5-tribromobenzene and 400 mL of diethyl ether,
followed by cooling to -78° C. At -78° C., 60 mL of a 1.6M
solution containing 96.0 mmol of n-butyllithium in hexane was added
dropwise by spending 1 hr, followed by aging at -78° C. for 1 hr.
After confirming lithiation by gas chromatography, 16.6 g (100.0 mmol) of
hexafluoroacetone was bubbled at -78° C., followed by stirring for
1 hr. After stirring, the reaction liquid was added to 400 mL of 2N
hydrochloric acid to separate it into an organic layer and an aqueous
layer. The aqueous layer was extracted with 100 mL of isopropyl ether.
The combined organic layer was dried with anhydrous magnesium sulfate,
followed by concentration with an evaporator and then solid distillation,
thereby obtaining 23.0 g of
1-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-3,5-dibromobenzene
(yield: 60%) represented by the following formula.

##STR00036##

[0228]The properties of
1-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-3,5-dibromobenzene
were as follows.

1H NMR (CDCl3): δ 7.79 (S, 3H).

19F NMR (CDCl3): δ -76.0 (S, 6F, CF3).

[0231]A 10 mL autoclave was charged with 1.00 g (2.6 mmol) of the obtained
1-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-3,5-dibromobenzene-
, 0.056 g (0.25 mmol) of palladium acetate, 0.263 g (1.0 mmol) of
triphenylphosphine, 1.01 g (10.0 mmol) of triethylamine, 0.50 g of water,
and 2.0 g of tetrahydrofuran. Then, the reaction was conducted at
100° C. for 17 hr under a carbon monoxide pressure of 2 MPa. After
the reaction, 5 mL of 2N hydrochloric acid was added to the reaction
liquid, followed by extraction with 5 mL of isopropyl ether to separate
an organic layer. To this organic layer 6 mL of 7% sodium hydroxide
aqueous solution was added to separate an aqueous layer. This aqueous
layer was washed with 3 mL of heptane, followed by adding 6 mL of 6N
hydrochloric acid. The precipitated solid was isolated by filtration and
then washed with 5 mL of heptane, thereby obtaining 0.35 g of
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid (yield: 41%) represented by the following formula.

##STR00037##

[0232]The properties of
5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarbo-
xylic acid were as follows.

1H NMR (CDCl3): δ 9.27 (S, 1H), 8.58 (t, 1H), 8.46 (s,
2H).

19F NMR (CDCl3): δ -73.5 (S, 6F, CF3).

EXAMPLE 4

Synthesis of Polymer 1

##STR00038##

[0236]A three-necked flask was charged with 2.00 g (6.0 mmol) of
Dicarboxylic Acid 2, 1.37 g (6.0 mmol) of bisphenol A, 4.19 g (12.6 mmol)
of triphenylphosphine dichloride as a condensing agent, and 12.0 g of
N-methyl-2-pyrrolidone (NMP), followed by stirring at room temperature
for 3 hr under nitrogen atmosphere. The obtained viscous solution was
added to 30 mL of methanol. The obtained precipitate was separated by
filtration, followed by vacuum drying at 80° C., thereby obtaining
2.84 g of Polymer 1 (yield: 91%). The result is shown in Table 1.

[0237]1.00 g of the obtained Polymer 1 and 4.00 g of N,N-dimethylformamide
(DMF) were mixed together to prepare a homogeneous solution. This
solution was filtered, and the filtrate was applied onto a glass
substrate by spin coating, followed by heating under nitrogen atmosphere
at 80° C. for 30 min, at 150° C. for 30 min, and at
250° C. for 1 hr, thereby obtaining a transparent film. After the
film was separated from the glass substrate, the film maintained its
shape. The properties of the film are shown in Table 2.

4.19 g (12.6 mmol) of triphenylphosphine dichloride as a condensing agent,
and 19.0 g of N-methyl-2-pyrrolidone (NMP), followed by the same steps as
those of Example 4, thereby obtaining Polymer 2 (yield: 90%). The result
is shown in Table 1.

[0240]1.00 g of the obtained Polymer 2 and 4.00 g of N,N-dimethylformamide
(DMF) were mixed together to prepare a homogeneous solution. This
solution was filtered, and the filtrate was applied onto a glass
substrate by spin coating, followed by heating under nitrogen atmosphere
at 80° C. for 30 min, at 150° C. for 30 min, and at
250° C. for 1 hr, thereby obtaining a transparent film. After the
film was separated from the glass substrate, the film maintained its
shape. The properties of the film are shown in Table 2.

4.19 g (12.6 mmol) of triphenylphosphine dichloride as a condensing agent,
and 20.0 g of N-methyl-2-pyrrolidone (NMP), followed by the same steps as
those of Example 4, thereby obtaining Polymer 3 (yield: 85%). The result
is shown in Table 1.

EXAMPLE 7

Synthesis of Polymer 4

##STR00043##

[0244]1.00 g of Polymer 3 obtained by Example 3 and 4.00 g of
N,N-dimethylformamide (DMF) were mixed together to prepare a homogeneous
solution. This solution was filtered, and the filtrate was applied onto a
glass substrate by spin coating, followed by heating under nitrogen
atmosphere at 80° C. for 30 min, at 150° C. for 30 min, at
250° C. for 30 min, and at 320° C. for 1 hr, thereby
obtaining a transparent film. After the film was separated from the glass
substrate, the film maintained its shape. The film was found to have a
structure of Polymer 4 by IR analysis. The properties of the film are
shown in Table 2.

4.19 g (12.6 mmol) of triphenylphosphine dichloride as a condensing agent,
and 26.0 g of N-methyl-2-pyrrolidone (NMP), followed by the same steps as
those of Example 4, thereby obtaining Polymer 5 (yield: 87%). The result
is shown in Table 1.

EXAMPLE 9

Synthesis of Polymer 6

##STR00046##

[0248]1.00 g of Polymer 5 obtained by Example 8 and 4.00 g of DMF were
mixed together to prepare a homogeneous solution. This solution was
filtered, and the filtrate was applied onto a glass substrate by spin
coating, followed by heating under nitrogen atmosphere at 80° C.
for 30 min, at 150° C. for 30 min, and at 250° C. for 1 hr,
thereby obtaining a transparent film. After the film was separated from
the glass substrate, the film maintained its shape. The film was found to
have a structure of Polymer 6 by IR analysis. The properties of the film
are shown in Table 2.

COMPARATIVE EXAMPLE 1

Synthesis of Polymer 7

##STR00047##

[0250]Example 4 was repeated except in that Dicarboxylic Acid 2 was
replaced with Dicarboxylic Acid 4 represented by the following formula.

##STR00048##

With this, a transparent film was obtained. After the film was separated
from the glass substrate, the film maintained its shape. The properties
of the film are shown in Table 2.

COMPARATIVE EXAMPLE 2

Synthesis of Polymer 8

##STR00049##

[0252]Example 5 was repeated except in that Dicarboxylic Acid 1 was
replaced with Dicarboxylic Acid 4 of Comparative Example 1. With this, a
transparent film was obtained. After the film was separated from the
glass substrate, the film maintained its shape. The properties of the
film are shown in Table 2.

COMPARATIVE EXAMPLE 3

Synthesis of Polymer 9

##STR00050##

[0254]Example 6 was repeated except in that Dicarboxylic Acid 3 was
replaced with Dicarboxylic Acid 4 of Comparative Example 1. The resulting
polymer was subjected to the same procedures as those of Example 7,
thereby obtaining a transparent film having a structure of Polymer 9.
After the film was separated from the glass substrate, the film
maintained its shape. The properties of the film are shown in Table 2.

COMPARATIVE EXAMPLE 4

Synthesis of Polymer 10

##STR00051##

[0256]Example 8 was repeated except in that Dicarboxylic Acid 3 was
replaced with Dicarboxylic Acid 4 of Comparative Example 1. The resulting
polymer was subjected to the same procedures as those of Example 9,
thereby obtaining a transparent film having a structure of Polymer 10.
After the film was separated from the glass substrate, the film
maintained its shape. The properties of the film are shown in Table 2.

[0257]It is understood from Table 2 that Polymers 1, 2, 4 and 6 according
to Examples 4, 5, 7 and 9, each polymer having a hexafluoroisopropanol
group, are respectively lower in dielectric constant and water absorption
than Polymers 7 to 10 according to Comparative Examples 1 to 4, each
polymer having a phenolic hydroxy group, in contrast with the
hexafluoroisopropanol group.

[0258]The entire contents of Japanese Patent Application No. 2007-185257
(filed Jul. 17, 2007), of which priority is claimed in the present
application, are incorporated herein by reference.